TWI266145B - Chemically amplified photoresist composition, photoresist layer laminate, manufacturing method for photoresist composition, manufacturing method for photoresist pattern and manufacturing method for connecting terminal - Google Patents
Chemically amplified photoresist composition, photoresist layer laminate, manufacturing method for photoresist composition, manufacturing method for photoresist pattern and manufacturing method for connecting terminal Download PDFInfo
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(1) 1266145 九、發明說明 【發明所屬之技術領域] 本發明係關於’增強化學性型光阻組成物,光阻層層 合體’光阻組成物之製造方法,光阻圖型之製造方法及連 接用端子之製造方法。進而詳言之,係關於對半導體或電 子部件之電路基板之實裝等所使用連接用端子之製造爲恰 當的’增強化學性型光阻組成物,光阻層層合體,光阻組 成物之製造方法’光阻圖型之製造方法及連接用端子之製 造方法。 【先前技術】 現在成爲精密微細加工技術主流之光製造裝置( photo fabrication)係指,使感光性樹脂組成物塗布於加 工物表面以形成塗膜,藉由光微影術技術使塗膜圖型化, 使其作爲光.罩進行以化學蝕刻,電解蝕刻及/或電鍍( electroplating)爲主體之電子成形(electro-forming), 以製造半導體封裝體等之各種精密部件之技術之總稱。 近年來隨著電子機器之小型化,半導體封裝體之高密 度實裝技術正持續進展中,進而謀求封裝體之多銷(pin )薄膜組裝(niouting )化,封裝體尺寸之小型化,正謀 求倒裝片(flip chip )方式之2次元組裝技術,3次元組 裝技術之組裝密度之提高。在此種高密度組裝技術中,連 接用端子係例如’在封裝體上突出之凸塊(bump )等之 突起電極(組裝端子)或,自晶圓上之周邊(peripheral (2) 1266145 )端子延伸之再配線與組裝端子予以連接之金屬柱體( metal post)等在基板上被闻精度地配置。 上述般之使用於光製造裝置之材料方面則有光阻。光 阻係,例如,使用於電鍍步驟所致凸塊或金屬柱體後之形 成等。凸塊或金屬柱體,例如,係在支持體上形成光阻, 透過所定之光罩圖型予以曝光,顯影,形成凸塊或金屬柱 體之部分被選擇性除去(剝離)之光阻圖型被形成,在此 被除去部分(非光阻部)可使銅等之導體被電鍍所埋入後 ,而可藉由除去其周圍之光阻圖型來形成。 在光阻方面,例如,在下述專利文獻1〜3,有記載 作爲凸塊形成或配線形成用之光聚合性之感光性樹脂組成 物。 一方面,與該等光聚合性之感光性樹脂組成物比較爲 高感度之感光性樹脂組成物方面,周知爲含有酸產生劑之 增強化學性型光阻。增強化學性型光阻之特徵,係藉由輻 射線照射(曝光),自酸產生劑可產生酸,藉由曝光後之 加熱處理可促進酸之發生,對於樹脂組成物中之基底樹脂 等會引起酸觸媒反應,而使其鹼溶解性變化。 在增強化學性型光阻,藉由輻射線照射,則有本爲鹼 不溶性者成爲鹼可溶化之正型與,本爲鹼可溶者成爲鹼不 溶化之負型。例如,在增強化學性型負型光阻之代表性例 方面,係在下述非專利文獻1,有記載將L.E. Bogan等人 之聚乙烯苯酚與三聚氫胺衍生物予以組合之光阻。 但是,使用上述增強化學性型光阻來製成光阻層之情 -6- 1266145 (3) 形’使用於基板等之支持體之,鋁,銅等之金屬,在光阻 層中會有對於樹脂之酸之作用阻礙之情形,會有無法獲得 所要求之商精度之光阻圖型特性之問題。 【專利文獻1】 日本特開平1 0-2 070 5 7號公報 【專利文獻2】 日本特開2000-39709號公報 【專利文獻3】 # 曰本特開2000-663 8 6號公報 【非專利文獻1】(1) 1266145 IX. Description of the Invention [Technical Field of the Invention] The present invention relates to a method for producing a photoresist film composition of a 'chemically enhanced photoresist composition, a photoresist layer laminate', and a photoresist pattern. And a method of manufacturing the terminal for connection. In addition, it is a 'reinforced chemical type photoresist composition, a photoresist layer laminated body, and a photoresist composition which are suitable for the manufacture of the connection terminal used for the mounting of the circuit board of semiconductor or electronic component. Manufacturing Method 'The manufacturing method of the photoresist pattern and the manufacturing method of the terminal for connection. [Prior Art] Photographing, which is currently the mainstream of precision microfabrication technology, means that a photosensitive resin composition is applied to a surface of a workpiece to form a coating film, and a coating film pattern is obtained by photolithography. A technique in which electrons are formed by chemical etching, electrolytic etching, and/or electroplating as a light-shield, and various precision parts such as semiconductor packages are manufactured. In recent years, with the miniaturization of electronic devices, the high-density mounting technology of semiconductor packages is continuing to progress, and the pin-up film assembly (niouting) of the package is required, and the size of the package is miniaturized. The two-dimensional assembly technique of the flip chip method improves the assembly density of the three-dimensional assembly technique. In such a high-density assembly technique, the terminal for connection is, for example, a bump electrode (assembly terminal) such as a bump protruding on the package or a peripheral (peripheral (2) 1266145) terminal on the wafer. A metal post or the like to which the extended rewiring and the assembly terminal are connected is accurately placed on the substrate. The above-mentioned materials used in the optical manufacturing apparatus have photoresist. The photoresist system is, for example, used for forming a bump or a metal post caused by an electroplating step. A bump or a metal pillar, for example, a photoresist formed by forming a photoresist on a support, exposing it through a predetermined mask pattern, developing, forming a bump or a portion of the metal pillar selectively removed (peeled) The type is formed, and the removed portion (non-photosensitive portion) can be formed by embedding a conductor such as copper after plating, and can be formed by removing the photoresist pattern around it. In the case of the photoresist, for example, the photopolymerizable photosensitive resin composition for forming a bump or forming a wiring is described in the following Patent Documents 1 to 3. On the other hand, the photosensitive resin composition having a high sensitivity as compared with the photopolymerizable photosensitive resin composition is known as a chemically-resistant photoresist containing an acid generator. The characteristic of enhancing the chemical type resist is that the acid is generated by the irradiation of radiation (exposure), and the acid can be generated by the heat treatment after the exposure, and the base resin in the resin composition is Causes acid catalyst reaction, and changes its alkali solubility. When the chemical-type resist is reinforced by irradiation with radiation, the base which is insoluble in alkali is a positive type which is solubilized by alkali, and the one which is alkali-soluble is a negative type in which alkali is insolubilized. For example, Non-Patent Document 1 discloses a photoresist which combines a polyvinyl phenol of L.E. Bogan et al. and a melamine derivative in a representative example of enhancing a chemical type negative resist. However, the above-mentioned enhanced chemical type photoresist is used to form the photoresist layer. -6- 1266145 (3) The shape is used for a support such as a substrate, and a metal such as aluminum or copper is present in the photoresist layer. In the case where the action of the acid of the resin is hindered, there is a problem that the photoresist pattern characteristic of the required commercial accuracy cannot be obtained. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. 2000-39709 [Patent Document 3] # 曰本特开 2000-663 8 No. 6 [Non-patent Literature 1]
Proceeding of SPIE,1 0 8 6 巻,3 4-47 頁(1 9 8 9 年) ' 【發明內容】 〔發明欲解決之課題〕 因此本發明,係爲解決上述習知技術之問題而完成者 ,其課題係提供一種可形成高精度光阻圖型之增強化學性 φ 型光阻組成物,使其在支持體上層合之光阻層層合體,光 阻組成物之製造方法,光阻圖型之製造方法,及連接用端 子之製造方法。 〔解決課題之手段〕 本發明人等經戮力檢討,結果,發現在習知增強化學 性型光阻組成物添加防銹劑而可解決上述課題,因而完成 本發明。 -7- (4) 1266145 亦即,本發明之第1態樣(a s p e c t )係含有, 由酸使鹼溶解性變化之樹脂,(b )藉由輻射線照 產生之化合物及(c )防銹劑,之增強化學性型光 物。 本發明之第2態樣(aspect )係,支持體與, 強化學性型光阻組成物所成光阻層,予以層合之光 合體。 本發明之第3態樣(aspect )係將,(a )因酸 解性變化之樹脂,(b )因輻射線照射使酸產生之 及(c )防銹劑,予以混合之增強化學性型光阻組 製造方法。 本發明之第4態樣(aspect )係含有,使前述 學性型光阻組成物層合於支持體而獲得光阻層層合 合步驟與,對該光阻層層合體予以選擇性照射輻射 光步驟與,在該曝光步驟後予以顯影以獲得光阻圖 影步驟,之光阻圖型之製造方法。 本發明之第5態樣(aspect )係含有,在使用 阻圖型製造方法所得光阻圖型之非光阻部之中,形 所成連接用端子之步驟,的連接用端子之製造方法 〔發明效果〕 根據本發明係提供,可獲得在輻射線照射前使 性不致變化之穩定增強化學性型光阻組成物,及使 組成物層合於支持體之光阻層層合體,使用其之光 (a)藉 射使酸 阻組成 前述增 阻層層 使鹼溶 化合物 成物之 增強化 體之層 線之曝 型之顯 前述光 成導體 鹼溶解 該光阻 阻圖型 -8- (5) 1266145 製造方法及連接用端子製造方法。 〔貫施發明之最佳形態〕 以下’關於本發明予以詳細說明。 本發明之增強化學性型光阻組成物在使用,(a )因 酸使驗溶解性變化之樹脂,(b )因輻射線照射使酸產生 之化合物’加上(c )防銹劑的話,爲正型或負型均可。 以下’以負型增強化學性型光阻組成物之例加以說明 (a )因酸使鹼溶解性變化之樹脂·· 增強化學性型光阻組成物爲負型之情形,(a )因酸 使鹼溶解性變化之樹脂(以下,稱爲(a )成分)係,因 酸使鹼溶解性降低之樹脂,一般若爲作爲負型增強化學性 型光阻之基底樹脂使用之樹脂則並無特別限定,因應使用 於曝光之光源,可自習知之物任意選擇使用。例如,以酸 醛淸漆樹脂爲主成分之物,因其特性良好,一般被廣泛使 用。 特佳之(a)成分方面’可例不選自(甲)g分醛淸漆 樹脂’及(乙)具有經基本乙如構成早7C之聚合物之1種 以上樹脂所成者。係因爲可谷易控制塗布性,顯影速度之 故。 (甲)酚醛淸漆樹脂(以下,稱爲(甲)成分)係, 例如具有苯酚性羥基之芳香族化合物(以下,單稱爲「苯 -9- (6) 1266145 酚類」)與醛類在酸觸媒下予以加成縮合而可獲得。 此際,所使用之苯酚類方面,可例舉例如苯酚,鄰甲 酚,間甲酚,對甲酚,鄰乙基苯酚,間乙基苯酚,對乙基 苯酚,鄰丁苯酚,間丁苯酚,對丁苯酚,2,3 -二甲苯酚 ,2,4一二甲苯酚,2,5—二甲苯酚,2,6 —二甲苯酚, 3,4 一二甲苯酚,3,5 —二甲苯酚,2,3,5 —三甲基苯 酚,3,4,5 —三甲基苯酚,對苯基苯酚,間苯二酚,氫 醌(hydroquinone),氫醌單甲基醚,五倍子酚,間苯三 酚,羥基二苯基,雙苯酚A,五倍子酸,五倍子酸酯,α 一萘酚,$ —萘酚等。 又醛類方面,可例舉例如甲醛,糠醛,苯甲醛,硝基 苯甲醛,乙醛等。< 加成縮合反應時之觸媒,並無特別限定,例如在酸觸 媒,可使用鹽酸,硝酸,硫酸,甲酸,草酸,乙酸等。 上述酚醛淸漆樹脂,以質量平均分子量爲 3000〜 10000,較佳爲 6000〜9000,進而較佳爲 7000〜8000之 範圍內者爲佳。質量平均分子量不足3 0 0 0時,顯影後會 有膜變薄之傾向,又,質量平均分子量超過10000時,在 顯影後會有殘渣殘留之傾向,並不佳。 在具有(乙)羥基苯乙烯構成單元之聚合物(以下, 稱爲(乙)成分)方面,可例舉例如,僅由對羥基苯乙烯 等之羥基苯乙烯,α —甲基羥基苯乙烯,α -乙基羥基苯 乙烯等之α -烷基羥基苯乙烯等之羥基苯乙烯構成單元所 成自由基聚合物或離子聚合物或,前述羥基苯乙烯構成單 -10- (7) 1266145 元與其以外之構成單元所成共聚物。聚合物中羥基苯乙烯 構成單元之比率,較佳爲1質量%以上,更佳爲1 0〜3 0 質量%。此係,羥基苯乙烯構成單元之比率不足1 0質量 %時,會有顯影性,解像性傾向於降低之故。 又,前述(乙)成分之質量平均分子量,較佳爲 500 0以下,更佳爲2〇〇〇以上4000以下。此係,質量平 均分子量超過5 0 0 0時會有解像性降低之傾向。 前述(乙)之構成單元’可含有形成前述羥基苯乙烯 構成單元以外之構成單元之單體。此種單體方面較佳者, 係使羥基苯乙烯構成單元之羥基以其他基取代之單體或具 有^ Θ —不飽和雙鍵之單體等。 可取代前述羥基苯乙烯構成單元之羥基之其他基方面 ’ β爲不被酸所解離之鹼溶解抑制基。 不被酸所解離之鹼溶解抑制基方面,可例舉可取代或 未取代之苯磺醯基氧基’取代或未取代之萘磺醯基氧基, 取代或未取代之苯羰氧基,取代或未取代之萘羰氧基等。 取代或未取代之苯磺醯基氧基之具體例方面,可例舉苯磺 酿基氧基,氯苯磺醯基氧基,甲基苯磺醯基氧基,乙基苯 基氧基,丙苯磺醯基氧基,甲氧苯磺醯基氧基,乙氧 本墙_基氧基,丙氧苯磺醯基氧基,乙醯胺基苯磺醯基氧 基等爲佳。又取代或未取代之萘磺醯基氧基之具體例方面 奈晴醯基氧基,氯萘磺醯基氧基,甲基萘磺醒基氧基, 2基奈磺酿基氧基’丙萘磺醯基氧基,甲氧萘磺醯基氧基 乙氧萘磺醯基氧基,丙氧萘磺醯基氧基,乙醯胺基萘磺 -11 . (8) 1266145 S盡基氧基等爲佳。進而,取代或未取代之苯羰氧基及取代 或未取代之萘羰氧基方面在前述之例中,可例舉將取代$ 未取代之磺醯基氧基置換成鑛氧基者爲佳。其中以,乙冑 胺基苯磺醯基氧基或乙醯胺基萘磺醯基氧基爲佳。 又,在具有^,/5 -不飽和雙鍵單體之具體例方面, 可例舉苯乙烯,氯苯乙烯,氯甲基苯乙烯,乙烯甲苯,α 一甲基苯乙烯等之苯乙烯系單體,丙烯酸甲酯,甲基两燦 酸甲酯,甲基丙烯酸苯酯等之丙烯酸單體,乙酸乙_, φ 安息香酸乙烯等之乙酸乙烯系單體等,但其中以苯乙燒爲 佳。由羥基苯乙烯與苯乙烯所得之共聚物,以例如聚(4 一羥基苯乙烯一苯乙烯)共聚物,聚(4 一羥基苯乙烯— . 甲基苯乙烯)共聚物等,在可顯示高解像性之同時,耐熱 ^ 性亦高爲佳。 進而,在(a )成分,於可使物理,化學特性予以適 度控制之目的下,可含有其他樹脂成分。例如可例舉(丙 )丙烯系樹脂,(丁)乙烯樹脂。 φ (丙)丙烯系樹脂: 爲(丙)成分之丙烯系樹脂,若爲鹼可溶性之丙烯系 樹脂則無特別限定,但尤以含有,具有醚鍵結之聚合性化 合物所衍生之構成單元,及具有羧基之聚合性化合物所衍 生之構成單元爲佳。 具有醚鍵結之聚合性化合物方面,可例示2 -甲氧基 乙基(甲基)丙烯酸酯,甲氧基三乙二醇(甲基)丙烯酸 -12- 0) 1266145 酯,3 —甲氧基丁(甲基)丙烯酸酯,乙基卡必醇(甲基 )丙緒酸酯,苯氧基聚乙二醇(甲基)丙烯酸酯,甲氧基 聚丙二醇(甲基)丙烯酸酯,四氫糠基(甲基)丙烯酸酯 等之具有酸鍵結及醋鍵結之(甲基)丙嫌酸衍生物等,較 佳爲’ 2 —甲氧基乙基丙烯酸酯,甲氧三乙二醇丙烯酸酯 。該等化合物可單獨或者組合2種以上使用。 具有羧基之聚合性化合物方面,可例示丙烯酸,甲基 丙烯酸,巴豆酸等之單羧酸,順丁烯二酸,反丁烯二酸, 伊康酸等之二羧酸,2一甲基丙烯醯基氧乙基琥珀酸,2一 甲基丙烯醯基氧乙基順丁烯二酸,2—甲基丙烯醯基氧乙 基反丁烯二酸,2—甲基丙烯醯基氧乙基六氫反丁烯二酸 等之具有羧基及酯鍵結之化合物等,較佳爲,丙烯酸,甲 基丙烯酸。該等化合物可單獨或者組合2種以上使用。 (丁)乙烯樹脂: 爲(丁)成分乙烯樹脂,係聚(乙烯低級烷基醚), 下述一般式(I )所示之乙烯低級烷基醚之單獨或2種以 上之混合物予以聚合所得之(共)聚合物所成。 化 Η C II 6 CIOIR Η N)/ I—I /(\ (上述一般式(Ο中,R6表示碳數1〜5之直鏈狀或者分 支鍵狀之院基。) 一般式(I )中,碳數1〜5之直鏈狀或者分支鏈狀之 -13- (10) 1266145 烷基方面,可例舉例如,甲基,乙基,正丙基,i 一丙基 ,正丁基,i - 丁基,正戊基,i 一戊基等。在該等烷基中 ,以甲基,乙基,i 一丁基爲佳,尤以甲基,乙基爲佳。 本發明中,特佳之聚(乙烯低級烷基醚)係,聚(乙烯甲 基醚),聚(乙烯乙基醚)。 另外,(a )成分在含有,(甲)成分與(乙)成分 之混合樹脂所成情形,係以(甲)成分與(乙)成分之總 和爲100質量份,(甲)成分爲50〜98質量份,較佳爲 55〜95質量份,(乙)成分爲50〜2質量份,較佳爲45 〜5質量份。 (b )因輻射線照射使酸產生之化合物 本發明所使用之(b )成分,係酸產生劑,若可由光 直接或者間接地使酸產生之化合物並無特別限定,但,具 體而言,可例舉 2,4一雙(三氯甲基)一 6_ [2 - (2 - 呋喃基)乙烯基]一 s-三畊,2,4一雙(三氯甲基)一6 一 [2 — (5 -甲基一2—呋喃基)乙烯基]—s —三畊,2,4 一雙(三氯甲基)一 6— [2 - (5 —乙基—2 —呋喃基)乙 烯基]—s —三啡,2,4一雙(三氯甲基)一 6— [2 - (5 - 丙基一2—呋喃基)乙烯基]—s —三畊,2,4一雙(三氯 甲基)一 6 — [2 — (3,5 —二甲氧苯基)乙烯基])—s- 三畊,2,4一雙(三氯甲基)一 6 — [2 — (3,5 —二乙氧 苯基)乙烯基]一 s —三畊,2,4一雙(三氯甲基)一6-[2— (3,5-二丙氧苯基)乙烯基]一 s-三哄,2,4一雙 -14- (11) 1266145 (三氯甲基)一 6— [2 — (3 —甲氧基一5 —乙氧苯基)乙 烯基]—s -三哄,2,4 —雙(三氯甲基)一 6 — [2— (3 — 甲氧基—5 —丙氧苯基)乙烯基]—s —三哄,2,4 —雙( 三氯甲基)一 6— [2 — (3,4 一亞甲基二氧苯基)乙烯基] —s —三畊,2,4 —雙(三氯甲基)一6— (3,4 —亞甲基 二氧苯基)一s —三畊,2,4 —雙一三氯甲基—6— (3 — 溴一4甲氧基)苯基一 s—三畊,2,4一雙一三氯甲基一6 一 (2 —溴一4甲氧基)苯基一 s—三哄,2,4一雙一三氯 甲基一 6 — (2 —溴一4 —甲氧基)苯乙烯基苯基—s —三畊 ,2,4 —雙一三氯甲基—6— (3 —溴一4甲氧)苯乙烯基 苯基一s —三畊,2— (4 —甲氧苯基)—4,6-雙(三氯 甲基)> 1,3 ’ 5 —三畊,2 — ( 4 —甲氧萘基)—4,6 — 雙(三氯甲基)一 1,3,5-三啡,2 — [2— (2 —呋喃基 )乙烯基]一 4,6—雙(三氯甲基)一 1,3,5 -三畊,2 —[2— (5 —甲基一2 -呋喃基)乙烯基]—4,6—雙(三 氯甲基)一1,3,5 —三畊,2 — [2— (3,5 —二甲氧苯基 )乙烯基]一 4,6 —雙(三氯甲基)一 1,3,5 —三畊,2 —[2_ (3,4 一二甲氧苯基)乙烯基]—4,6 —雙(三氯 甲基)一1,3,5—三哄,2— (3,4 —亞甲基二氧苯基) —4,6—雙(三氯甲基)一 1,3,5 —三哄,三(1,3-二溴丙基)一 1,3,5 —三哄,三(2,3 —二溴丙基)—1 ,3,5—三畊等之含鹵素三畊化合物及三(2,3 —二溴丙 基)異三聚氰酸酯等之下述-般式所示含鹵素三畊化合物 -15- 1266145Proceeding of SPIE, 1 0 8 6 巻, 3 4-47 (1 9 8 9) ' [Summary of the Invention] The present invention has been made to solve the above problems of the prior art. The subject of the invention is to provide a photoreceptive layer laminate which can form a high-precision photoresist pattern and which can be laminated on a support, a photoresist composition, a photoresist pattern, and a photoresist pattern. A manufacturing method of the type and a manufacturing method of the terminal for connection. [Means for Solving the Problems] As a result of intensive review, the inventors of the present invention have found that the above-mentioned problems can be solved by adding a rust inhibitor to a conventional reinforced chemical resist composition, and thus the present invention has been completed. -7- (4) 1266145 That is, the first aspect of the present invention contains a resin which changes solubility of an alkali by an acid, (b) a compound which is irradiated by radiation, and (c) rust prevention. An agent that enhances chemical light species. The second aspect of the present invention is a composite in which a support and a photoresist layer formed of a strong chemical resist composition are laminated. The third aspect of the present invention is a chemically enhanced type in which (a) a resin which changes in acid solubility, (b) an acid generated by radiation irradiation, and (c) a rust preventive agent. Photoresist group manufacturing method. A fourth aspect of the present invention includes a step of laminating the above-mentioned physico-type photoresist composition to a support to obtain a photoresist layer, and selectively irradiating the photoresist layer The photo-step and the method of manufacturing the photoresist pattern after the exposure step to obtain a photoresist pattern step. The fifth aspect of the present invention includes a method of manufacturing a terminal for connection in which a terminal for forming a connection is formed in a non-photoresist portion of a resist pattern obtained by a resistive pattern manufacturing method. Advantageous Effects of Invention According to the present invention, it is possible to obtain a stable-enhanced chemical-type resist composition in which the properties are not changed before irradiation of radiation, and a photoresist layer laminate in which a composition is laminated on a support, and the same is used. The light (a) is caused by the acid resistance to form the above-mentioned resistance-increasing layer layer, so that the exposed layer of the alkali-soluble compound is enhanced, and the photo-conductor is dissolved in the photo-resistance pattern - 8 - (5 1266145 Manufacturing method and method of manufacturing terminal for connection. [Best Mode of the Invention] Hereinafter, the present invention will be described in detail. When the chemically-resistant photoresist composition of the present invention is used, (a) a resin which changes solubility due to an acid, and (b) a compound which generates an acid by radiation irradiation plus (c) a rust preventive agent, It can be either positive or negative. The following description will be made by taking an example of a negative-type enhanced chemical resist composition (a) a resin which changes alkali solubility due to an acid, and a chemical-type resist composition which is a negative type, (a) acid A resin which changes the alkali solubility (hereinafter referred to as a component (a)), and a resin which is reduced in alkali solubility by an acid is generally not used as a resin which is a base resin which is a negative-type chemically-resistant photoresist. It is particularly limited, and it can be used arbitrarily from the conventional materials in view of the light source used for exposure. For example, an acid aldehyde lacquer resin as a main component is generally widely used because of its good characteristics. The component (a) is particularly preferably selected from the group consisting of (a) g-formaldehyde lacquer resin and (b) one or more resins having a basic composition of a polymer such as 7C. Because it is easy to control the coating properties and development speed. (A) phenolic enamel resin (hereinafter referred to as (meth) component), for example, an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "benzene-9-(6) 1266145 phenol)") and an aldehyde It can be obtained by addition condensation condensation under an acid catalyst. In this case, examples of the phenol to be used include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol. , p-butyrrol, 2,3-xylenol, 2,4-dimethylphenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-two Cresol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, gallicol , phloroglucinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, $-naphthol and the like. Further, examples of the aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde and the like. < The catalyst for the addition condensation reaction is not particularly limited. For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid or the like can be used as the acid catalyst. The above phenolic enamel resin is preferably a mass average molecular weight of from 3,000 to 10,000, preferably from 6,000 to 9000, more preferably from 7,000 to 8,000. When the mass average molecular weight is less than 30,000, the film tends to become thin after development, and when the mass average molecular weight exceeds 10,000, the residue tends to remain after development, which is not preferable. In the case of a polymer having a (i) hydroxystyrene structural unit (hereinafter referred to as a (B) component), for example, hydroxystyrene such as p-hydroxystyrene or α-methylhydroxystyrene may be mentioned. a radical polymer or an ionic polymer formed by a hydroxystyrene unit such as α-alkylhydroxystyrene or the like, or the above-mentioned hydroxystyrene constitutes a mono-10-(7) 1266145 Copolymers formed by other constituent units. The ratio of the hydroxystyrene constituent unit in the polymer is preferably 1% by mass or more, more preferably 10% to 30% by mass. When the ratio of the hydroxystyrene structural unit is less than 10% by mass, the developability is lowered and the resolution tends to be lowered. Further, the mass average molecular weight of the component (B) is preferably 500 or less, more preferably 2 to 4,000. In this system, when the mass average molecular weight exceeds 5,000, the resolution tends to decrease. The constituent unit (b) of the above (B) may contain a monomer which forms a constituent unit other than the constituent unit of the above hydroxystyrene. The monomer is preferably a monomer in which a hydroxyl group of a hydroxystyrene unit is substituted with another group or a monomer having a ?-unsaturated double bond. Other bases which may be substituted for the hydroxyl group of the above-mentioned hydroxystyrene structural unit ‘β is an alkali dissolution inhibiting group which is not dissociated by an acid. The base dissolution inhibiting group which is not dissociated by an acid may, for example, be a substituted or unsubstituted phenylsulfonyloxy 'substituted or unsubstituted naphthosulfonyloxy group, a substituted or unsubstituted phenylcarbonyloxy group, Substituted or unsubstituted naphthylcarbonyloxy group and the like. Specific examples of the substituted or unsubstituted benzenesulfonyloxy group include a phenylsulfonyloxy group, a chlorobenzenesulfonyloxy group, a methylbenzenesulfonyloxy group, and an ethylphenyloxy group. The propyl sulfonyloxy group, the methoxybenzenesulfonyloxy group, the ethoxy group wall oxy group, the propoxy sulfonyloxy group, the acetaminophen benzene sulfonyloxy group and the like are preferred. Specific examples of the substituted or unsubstituted naphthosulfonyloxy group, neatsyloxy, chloronaphthalenesulfonyloxy, methylnaphthalenesulfonyloxy, 2-methylsulfonyloxy-propyl Naphthalenesulfonyloxy, methoxynaphthalenesulfonyloxyethoxynaphthalenesulfonyloxy, propoxynaphthalenesulfonyloxy, acetaminonaphthalenesulfon-11. (8) 1266145 S-based oxygen Base is better. Further, in the above-mentioned examples, the substituted or unsubstituted phenylcarbonyloxy group and the substituted or unsubstituted naphthalenecarbonyloxy group are preferably those in which the substituted unsubstituted sulfonyloxy group is replaced by a mineral oxygen group. . Among them, an acetamidophenylsulfonyloxy group or an ethenylnaphthalenesulfonyloxy group is preferred. Further, specific examples of the monomer having a ^,/5-unsaturated double bond may, for example, be styrene, chlorostyrene, chloromethylstyrene, vinyltoluene or α-methylstyrene. Monomer, methyl acrylate, methyl bis-formic acid methyl ester, phenyl methacrylate acrylate monomer, acetic acid B _, φ benzoic acid ethylene and other vinyl acetate monomers, etc. good. a copolymer obtained from hydroxystyrene and styrene, for example, a poly(4-hydroxystyrene-styrene) copolymer, a poly(4-hydroxystyrene-methyl styrene) copolymer, etc., which can exhibit high At the same time as the resolution, the heat resistance is also high. Further, the component (a) may contain other resin components for the purpose of appropriately controlling physical and chemical properties. For example, a (propylene) propylene resin or a (butyl) vinyl resin can be exemplified. Φ (propylene) propylene-based resin: a propylene-based resin which is a component (c), and is not particularly limited as long as it is an alkali-soluble propylene-based resin, and particularly contains a constituent unit derived from a polymerizable compound having an ether bond. It is preferred that the constituent unit derived from the polymerizable compound having a carboxyl group is used. The polymerizable compound having an ether bond can be exemplified by 2-methoxyethyl (meth) acrylate, methoxy triethylene glycol (meth) acrylate -12- 0) 1266145 ester, 3-methoxy Butyl (meth) acrylate, ethyl carbitol (methyl) propyl acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, four a (meth)acrylic acid derivative such as hydroquinone (meth) acrylate or the like having an acid bond and an vinegar bond, preferably a 2-methoxyethyl acrylate or a methoxy triethylene group. Alcohol acrylate. These compounds may be used alone or in combination of two or more. Examples of the polymerizable compound having a carboxyl group include a monocarboxylic acid such as acrylic acid, methacrylic acid or crotonic acid, a dicarboxylic acid such as maleic acid, fumaric acid or itaconic acid, and 2-methylpropene. Mercaptooxyethyl succinic acid, 2-methylpropenyl oxyethyl maleic acid, 2-methylpropenyl oxyethyl fumarate, 2-methylpropenyl oxyethyl A compound having a carboxyl group and an ester bond, such as hexahydrofumaric acid, is preferably acrylic acid or methacrylic acid. These compounds may be used alone or in combination of two or more. (butyl) vinyl resin: a (butyl) component vinyl resin, a poly(ethylene lower alkyl ether), an ethylene lower alkyl ether represented by the following general formula (I), or a mixture of two or more thereof obtained by polymerization Made of (co)polymer. Η C II 6 CIOIR Η N) / I—I / (\ (The above general formula (Ο, R6 represents a linear or branched bond of the carbon number 1 to 5). General formula (I) In the case of a linear or branched chain of -1 to 5 carbon atoms of 1 to 5, the alkyl group may, for example, be a methyl group, an ethyl group, a n-propyl group, an i-propyl group or an n-butyl group. i - butyl, n-pentyl, i-pentyl, etc. Among these alkyl groups, a methyl group, an ethyl group, an i-butyl group is preferred, and a methyl group or an ethyl group is preferred. Particularly preferred poly(ethylene lower alkyl ether), poly(vinyl methyl ether), poly(vinyl ethyl ether). Further, component (a) contains a mixed resin of (a) component and (b) component. In the case, the sum of the (a) component and the (b) component is 100 parts by mass, the (meth) component is 50 to 98 parts by mass, preferably 55 to 95 parts by mass, and the (b) component is 50 to 2 mass. The portion is preferably 45 to 5 parts by mass. (b) The compound which is produced by irradiation of radiation to the acid (b) component used in the present invention is an acid generator which can be directly or indirectly caused by light. The compound is not particularly limited, and specific examples thereof include 2,4-bis(trichloromethyl)-6-[2-(2-furanyl)vinyl]-s-three-plow, 2, 4 Bis(trichloromethyl)-6-[2-(5-methyl-2-oxafuryl)vinyl]-s-three tillage, 2,4-bis(trichloromethyl)-6-[2- (5-ethyl-2-furyl)vinyl]-s-trimorphine, 2,4-bis(trichloromethyl)-6-[2-(5-propyl-2-furanyl)vinyl ]-s - three tillage, 2,4 double (trichloromethyl)-6 - [2 - (3,5-dimethoxyphenyl)vinyl])-s-three tillage, 2,4 pair (trichloromethyl)-6-[2 - (3,5-diethoxyphenyl)vinyl]-s-three tillage, 2,4-bis(trichloromethyl)-6-[2-( 3,5-dipropoxyphenyl)vinyl]-s-triazine, 2,4-bis-14-(11) 1266145 (trichloromethyl)-6-[2 - (3-methoxyl- 5-ethoxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-propoxyphenyl)vinyl] —s — three, 2 ,4-bis(trichloromethyl)-6-[2-(3,4-monomethylenedioxyphenyl)vinyl]-s-three-plowed, 2,4-bis(trichloromethyl)- 6-(3,4-methylenedioxyphenyl)-s-three tillage, 2,4-bis-trichloromethyl-6-(3-bromo-tetramethoxy)phenyl-s-three Plough, 2,4-bis-trichloromethyl- 6-(2-bromo-tetramethoxy)phenyl-s-trisyl, 2,4-di-mono-trichloromethyl-6-(2-bromo 4-1,4-methoxystyrylphenyl-s-three tillage, 2,4-bis-trichloromethyl-6-(3-bromo-tetramethoxy)styrenephenyl-s-three tillage ,2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)> 1,3 '5-three tillage, 2 —( 4 —methoxynaphthyl)-4,6 — double (trichloromethyl)-1,3,5-trimorphine, 2 —[2-(2-furyl)vinyl]- 4,6-bis(trichloromethyl)-1,3,5-three Plowing, 2-[2-(5-methyl-2-furanyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2 — [2— (3 ,5-dimethoxyphenyl)vinyl]-4,6 - bis(trichloromethyl)-1,3,5-three tillage, 2-[2_(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1 , 3,5-triazine, 2-(3,4-methylenedioxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, three (1,3 -Dibromopropyl)-1,3,5-triazine, tris(2,3-dibromopropyl)-1,3,5-three tillage, etc., halogen-containing three-till compounds and three (2,3- Halogenated three-till compound -15- 1266145 of the following general formula of dibromopropyl)isocyanate
R3 丫、R2 Ο (式中,R1〜R3表示,各自可爲相同或相異,之鹵化院 基) α — (對甲苯磺醯基氧亞胺基)一苯基乙腈,α —( 苯擴醯基氧亞胺基)一 2,4一二氯苯基乙腈,α -(苯磺 釀基氧亞胺基)一 2,6 — 一氯苯基乙膳,α —(2-氯苯 磺醯基氧亞胺基)一 4一甲氧苯基乙腈,α — (乙基磺醯 基氧亞胺基)- 1 -環戊烯基乙腈,下述一般式所示化合 物; 〔化3〕R3 丫, R2 Ο (wherein, R1 to R3 represent each, which may be the same or different, and the halogenated compound base) α - (p-toluenesulfonyloxyimino)-phenylacetonitrile, α - (benzene expansion醯-based oxyimino)- 2,4-dichlorophenylacetonitrile, α-(phenylsulfonyloxyimino)- 2,6-monochlorophenylethane, α-(2-chlorobenzenesulfonate)醯 methoxyiminoimido)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, a compound of the following general formula; [Chemical 3]
r4^c=n-o—so2r5 CN (式中,R4表示,一價〜三價有機基,R5表示取代,未 取代之飽和烴基,不飽和烴基或芳香族性化合物基,η表 示1〜3之自然數。 在此所謂芳香族性化合物基係指,在芳香族化合物顯 示特有物理化學性質之化合物之基,例如苯基,萘基等之 芳香族烴基或,呋喃基,噻吩基等之雜環基。該等在環上 可具有一個以上適當的取代基,例如鹵原子,烷基,烷氧 基,硝基等。又,R5以碳數1〜4之烷基特佳,可例舉甲 -16- (13) 1266145 基,乙基,丙基,丁基。尤其是R4以芳香族性化合物基 ,R5以低級烷基之化合物爲佳。在上述一般式所示之酸 產生劑方面,在n=l之時,R4爲苯基,甲基苯基,甲氧 苯基之任-種,R5爲甲基之化合物,具體而言可例舉α —(甲基磺醯基氧亞胺基)—1—苯基乙腈,α — (甲基 磺醯基氧亞胺基)—1 一 (對甲基苯基)乙腈,α — (甲 基磺醯基氧亞胺基)一 1 一(對甲氧苯基)乙腈。η=2時 ,上述一般式所示之酸產生劑方面,具體而言可例舉下述 化學式所示酸產生劑。) -17- 1266145 (14) 〔化4〕R4^c=no—so2r5 CN (wherein R4 represents a monovalent to trivalent organic group, R5 represents a substituted, unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic compound group, and η represents a nature of 1 to 3 The term "aromatic compound group" as used herein means a group of a compound exhibiting a specific physicochemical property in an aromatic compound, for example, an aromatic hydrocarbon group such as a phenyl group or a naphthyl group or a heterocyclic group such as a furyl group or a thienyl group. The ring may have one or more suitable substituents on the ring, such as a halogen atom, an alkyl group, an alkoxy group, a nitro group, etc. Further, R5 is particularly preferably an alkyl group having 1 to 4 carbon atoms, and may be exemplified as A- 16-(13) 1266145, ethyl, propyl, butyl. In particular, R4 is an aromatic compound group, and R5 is preferably a lower alkyl compound. In the above general formula, the acid generator is When n=l, R4 is a compound of a phenyl group, a methylphenyl group, a methoxyphenyl group, and R5 is a methyl group, and specifically, α-(methylsulfonyloxyimino group) ) 1-phenylacetonitrile, α - (methylsulfonyloxyimino)-1 mono(p-methylphenyl)acetonitrile, α — (Methylsulfonyloxyimino)-l-(p-methoxyphenyl)acetonitrile. When η=2, the acid generator represented by the above general formula may specifically be represented by the following chemical formula. Acid generator.) -17- 1266145 (14) [Chemical 4]
=N—Ο一S—CH3 d;N °2=N—Ο一S—CH3 d; N °2
C2H5—S—〇—N 〇2 =C—C=N-CN ύΝ Ό一S~C2H5 〇2 C4H9—S—〇—N=C 〇2 *C2H5—S—〇—N 〇2 =C—C=N-CN Ό Ό一 S~C2H5 〇2 C4H9—S—〇—N=C 〇2 *
;=N—〇~S—CF〇 iN;=N—〇~S—CF〇 iN
F〇C—S一O~N=CF〇C—S_O~N=C
i,N 雙(對甲苯磺醯基)重氮甲烷,雙(1,1 一二甲基乙 基磺醯基)重氮甲烷,雙(環己基磺醯基)重氮甲烷,雙 (2,4 一二甲基苯基磺醯基)重氮甲烷等之雙磺醯基重氮 甲烷類;對甲苯磺酸2 —硝苄基,對甲苯磺酸2,6 —二硝 苄基,硝苄基甲苯磺酸鹽,二硝苄基甲苯磺酸鹽,硝苄基 磺酸鹽,硝苄基碳酸酯,二硝苄基碳酸酯等之硝〒基衍生 物;五倍子酚三甲磺醯酯(mesylate ),五倍子酚三甲苯 -18- 1266193137231號專利申請案 中文說明書修正頁 (15) : 磺酸鹽,苄基甲苯磺酸鹽,苄基磺酸鹽,N—甲基磺醯基 氧琥珀醯亞胺,N-三氯甲基磺醯基氧琥珀醯亞胺,N-苯基磺醯基氧順丁烯二醯亞胺,N-甲基磺醯基氧鄰苯二 甲醯亞胺等之磺酸酯;N-羥基鄰苯二甲醯亞胺,N—羥 基苯二甲醯亞胺等之三氟甲烷磺酸酯;二苯基碘鑰六氟磷 酸鹽,(4 —甲氧苯基)苯基碘鑰三氟甲烷磺酸鹽,雙( 對三級丁苯基)碘鑰三氟甲烷磺酸鹽,三苯基鎏六氟磷酸 鹽,(4 一甲氧苯基)二苯基鎏三氟甲烷磺酸鹽,(對三 級丁苯基)二苯基鎏三氟甲烷磺酸鹽等之鑰鹽;安息香甲 苯磺酸鹽,α -甲基安息香甲苯磺酸鹽等之安息香甲苯磺 酸鹽類;其他之二苯基碘鍚鹽,三苯基鎏鹽,苯基重氮鐡 鹽,苄基碳酸酯等 (b )成分方面,可單獨使用該等之化合物,亦可組 合2種以上使用。 本發明之組成物中,此(b )成分之含量,相對於(a )成分1〇〇質量份,以〇·1〜20質量份之範圍爲佳。此( b)成分之含量不足〇·1質量份時會有感度不充分之虞’ 超過20質量份時則無法獲得均勻的光阻組成物,顯影性 亦會有降低之虞。在考慮感度,光阻組成物之均勻性及顯 影性等時,此(b )成分之較佳含量,係在5〜1 5質量份 之範圍。 (c )成分之防銹劑’相對於基板或者配線所使用之 金屬原子,尤其是相對於A1或Cu若爲可防止腐蝕者,則 並無特別限定,但可恰當地使用三丁胺’三戊胺,苯并三 -19- 1266145 (16) 物苯 合述 J 化上 5 系 化 唑 } ti,N bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(2, 4- dimethylphenylsulfonyl) diazomethane diazomethane such as diazomethane; 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, nitrile N-toluenesulfonate, dinitrobenzyl tosylate, nitric acid sulfonate, nitrobenzyl carbonate, dinitrobenzyl carbonate, etc.; ninthyl phenol trimethoprim (mesylate) ), gallic phenol trimethylbenzene-18-1266193137231 patent application Chinese manual revision page (15): sulfonate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyloxy amber Amine, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxybutylimide, N-methylsulfonyloxyphthalimide, etc. Sulfonate; N-hydroxyphthalimide, trifluoromethanesulfonate such as N-hydroxyphthalimide; diphenyl iodine hexafluorophosphate, (4-methoxyphenyl) Phenyl iodide Methanesulfonate, bis(p-tert-butylphenyl) iodine trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate , (for tertiary butylphenyl) diphenyl sulfonium trifluoromethanesulfonate and other key salts; benzoin tosylate, α-methylbenzoin tosylate and other benzoin tosylate; other In the case of the component (b) such as a diphenyl iodonium salt, a triphenyl sulfonium salt, a phenyldiazonium salt or a benzyl carbonate, the compounds may be used singly or in combination of two or more. In the composition of the present invention, the content of the component (b) is preferably in the range of from 1 to 20 parts by mass based on 1 part by mass of the component (a). When the content of the component (b) is less than 1 part by mass, the sensitivity is insufficient. When the content is more than 20 parts by mass, a uniform photoresist composition cannot be obtained, and the developability is also lowered. The content of the component (b) is preferably in the range of 5 to 15 parts by mass in consideration of sensitivity, uniformity and development of the photoresist composition, and the like. The metal rust agent of the component (c) is not particularly limited as long as it can prevent corrosion with respect to the metal atom used for the substrate or the wiring, but tributylamine can be suitably used. Pentylamine, benzotris-19- 1266145 (16) Benzene combined with J, 5 azoles} t
式 般 I 述 下 舉 例 可 〔式中,R1 ,R14表示,各自獨立之氫原子,取代或者非 取代之碳原子數1〜10之烴基,羧基,氨基,羥基,氰基 ,甲醯基,磺醯基烷基,或磺(sulf〇 )基;Q可例舉氫原 子’羥基’取代或者非取代之碳原子數1〜1 0之烴基(但 ,其構造中可具有醯胺鍵結,酯鍵結),芳基,或表示下 述式(III ) 〔化6〕 Κ:Formula I can be exemplified by the following formula: wherein R1 and R14 represent independently hydrogen atoms, substituted or unsubstituted hydrocarbon groups having 1 to 10 carbon atoms, carboxyl group, amino group, hydroxyl group, cyano group, methyl group, sulfonate. a mercaptoalkyl group or a sulfonyl group; Q may be a hydrocarbon group having a hydrogen atom 'hydroxyl group' substituted or unsubstituted and having 1 to 10 carbon atoms (however, the structure may have a mercapto bond, an ester Bonding), aryl, or representing the following formula (III) [Chem. 6] Κ:
Rj—Ν' r9 (III)Rj—Ν' r9 (III)
(式(III)中,R7表示碳原子數1〜6之烷撐基;R8,R9表 示,各自獨立之,氫原子,羥基,或碳原子數1〜6之羥 基烷基或者烷氧烷基)所示基〕所示苯并***系化合物。 「烴基」係,碳原子與氫原子所成有機基。本發明中 ,在上述基Q,Ri3,Rm之各定義中,烴基方面,可爲芳 香族烴基或脂肪族烴基之任一種,又可具有飽和,不飽和 鍵結,進而可爲直鏈,分支鏈之任一種。取代烴基方面’ -20- 1266145 (17) 可例示例如羥基烷基,烷氧烷基等。(In the formula (III), R7 represents an alkylene group having 1 to 6 carbon atoms; and R8 and R9 each independently represent a hydrogen atom, a hydroxyl group, or a hydroxyalkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group; a benzotriazole-based compound represented by the group]. The "hydrocarbon group" is an organic group formed by a carbon atom and a hydrogen atom. In the present invention, in the definition of the above-mentioned group Q, Ri3, and Rm, the hydrocarbon group may be either an aromatic hydrocarbon group or an aliphatic hydrocarbon group, or may have a saturated or unsaturated bond, and may be a straight chain or a branch. Any of the chains. The substituted hydrocarbon group '-20- 1266145 (17) can be exemplified by, for example, a hydroxyalkyl group, an alkoxyalkyl group or the like.
又,在C11所形成之基板之情形,在上述一般式(Π )中,Q方面尤以上述式(ΙΠ)所示基爲佳。其中,式( III )中,R8,R9係以選擇,各自獨立之,碳原子數1〜6 之羥基烷基或者烷氧烷基爲佳。另外,在R8,R9之至少 任一方爲碳原子數1〜6之烷基情形,相關組成之苯并三 唑系化合物之物性,因缺乏水溶性,使該化合物予以溶解 之其他成分在處理液中存在之情形,可恰當的使用。 又上述一般式(I)中,Q方面,可恰當地使用可顯 示水溶性之基者。具體而言,以氫原子,碳原子數1〜3 之烷基(亦即’甲基,乙基,丙基,異丙基),碳原子數 1〜3之經基烷基,羥基等,在基板上具有無機材料層( 例如’聚砍膜,無定形矽膜,等)之情形,就其防蝕性之 點而言較佳。Further, in the case of the substrate formed by C11, in the above general formula (Π), the Q is particularly preferably a group represented by the above formula (ΙΠ). Among them, in the formula (III), R8 and R9 are preferably selected from each other, and a hydroxyalkyl group or an alkoxyalkyl group having 1 to 6 carbon atoms is preferred. Further, in the case where at least one of R8 and R9 is an alkyl group having 1 to 6 carbon atoms, the physical properties of the benzotriazole-based compound having a relevant composition are such that the other component which dissolves the compound due to lack of water solubility is in the treatment liquid. The situation exists in the case and can be used properly. Further, in the above general formula (I), in the case of Q, those which exhibit water solubility can be suitably used. Specifically, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (that is, 'methyl, ethyl, propyl, isopropyl), a transalkyl group having 1 to 3 carbon atoms, a hydroxyl group, etc. In the case of having an inorganic material layer (for example, 'poly-cracked film, amorphous ruthenium film, etc.) on the substrate, it is preferable in terms of its corrosion resistance.
在苯并***系化合物方面,具體而言,例如苯并*** ,5,6—二甲基苯并***,丨一羥基苯并***,丨一甲基苯 并二卩坐,1 一氨基苯并三卩坐,1 一苯基苯并三卩坐,1 一經基 甲基本并二唑,1 一苯并***羧酸甲基,5 -苯并***羧酸 ,1 一甲氧〜苯并***,1一(2,2—二羥基乙基)一苯并 二唑,1 一 (2,3 -二羥基丙基)苯并***,或「 Ilkamate」系列係以千葉特用化學品公司所販售者爲主, 例舉2’2〜{[(4一甲基一 1H—苯并***一 ! 一基) 甲基]亞胺基}雙乙醇,2,广-U(5 -甲基-1H -苯并 二〇坐—1 一基)甲基]亞胺基}雙乙醇,2, — {[(4—甲 -21 - 1266145 (18) 基一 1H —苯并***一 1 一基)甲基]亞胺基丨雙乙烷,或2 ,2 {[(4 一甲基一1H —苯并***一 1 一基)甲基]亞胺 基}雙丙烷等。該等中,以1 一(2,3 —二羥基丙基)— 苯并***,2,2,一 {[(4 —甲基—1H—苯并***一 1—基 )甲基]亞胺基}雙乙醇,2,2 — — {[(5 —甲基一1H—苯 并***- 1 一基)甲基]亞胺基}雙乙醇等可恰當的使用。 可使用苯并***系化合物1種或2種以上。 在上述含硫化合物方面,可例舉二硫二甘油 [S ( CH2CH ( OH) CH2 ( OH) ) 2],雙(2,3 —二羥基丙 硫代)乙烯[CH2CH2 ( SCH2CH ( OH ) CH2 ( OH ) ) 2],3 一(2,3 —二羥基丙硫代)—2—甲基一丙磺酸鈉 [CH2 ( OH ) CH ( OH) CH2SCH2CH ( CH3 ) CH2S03Na],1 —硫甘油[HSCH2CH(OH) CH2 ( OH ) ],3 —氫硫基—1 一丙烷磺酸鈉[HSCH2CH2CH2S03Na],2 —氫硫基乙醇 [HSCH2CH2 ( OH )],氫硫基乙酸[HSCH2C02H],及 3 — 氫硫基—1—丙醇[HSCH2CH2CH20H],1,3,5 —三畊—2 ,4,6 —三硫醇等。該等中,可恰當地使用1 一硫甘油, 1,3,5 —三畊—2,4,6 -三硫醇,氫硫基乙酸等。 (c )成分可使用1種或2種以上。 (c)成分係相對於(a)成分100質量份,以0.0 1〜 5質量份之範圍爲佳,尤其是〇.1〜1質量份之範圍爲佳。 此(c )成分之含量在不足〇. 〇 1質量份時’會有無法獲得 高精度之光阻圖型之虞,超過5質量份時’會有光阻圖型 與基板之密接性降低之虞。 -22- 1266145 (19) 增強化學性型光阻組成物爲負型之情形,除了上述之 成分以外,進而,含有交聯劑。 本發明所使用之交聯劑方面,並無特別限制,可自使 用於周知之任意增強化學性型負型光阻組成物之交聯劑適 宜選擇使用。可使用例如三聚氫胺樹脂,尿素樹脂,鳥糞 胺(guanamine )樹脂,甘脲(glycoluril ) -甲醒樹脂, 琥珀醯醯胺-甲醛樹脂,乙烯尿素-甲醛樹脂等,但尤以 烷氧甲基化三聚氫胺樹脂或烷氧甲基化尿素樹脂等之烷氧 甲基化氨基樹脂等可恰當使用。前述烷氧甲基化氨基樹脂 係’例如,在沸騰水溶液中使三聚氫胺或尿素,與甲醛水 反應所得之縮合物,以甲基醇,乙基醇,丙醇,丁醇,異 丙醇等之低級醇類醚化,接著使反應液冷卻析出來製造。 在前述烷氧甲基化氨基樹脂方面,具體而言可例舉甲氧甲 基化三聚氫胺樹脂,乙氧甲基化三聚氫胺樹脂,丙氧甲基 化三聚氫胺樹脂,丁氧甲基化三聚氫胺樹脂,甲氧甲基化 ®素樹脂,乙氧甲基化尿素樹脂,丙氧甲基化尿素樹脂, 丁氧甲基化尿素樹脂等。前述烷氧甲基化氨基樹脂可單獨 使用’或組合2種以上使用。尤其是烷氧甲基化三聚氫胺 棱f脂,相對於輻射線之照射量之變化之光阻圖型之尺寸變 化量小,因可形成穩定之光阻圖型故佳。其中以,甲氧甲 ®化三聚氫胺樹脂,乙氧甲基化三聚氫胺樹脂,丙氧甲基 t Ξ聚氫胺樹脂及丁氧甲基化三聚氫胺樹脂爲佳。 前述交聯劑,相對於(a ) , ( b )及(c )成分之總 量1 〇〇質量份,以含有1〜3 0質量份之範圍爲佳。交聯劑 -23- 1266145 (20) 在不足1質量份時,所得之膜之耐電鍍性,耐藥品性,密 接性之降低或,所形成之凸塊形狀會有.不良之情況並不佳 ’又超過3 0質量份時,會有顯影時產生顯影不良之情形 ,並不佳。 在本發明之增強化學性型光阻組成物,在不損及本質 特性之範圍,進而可依照所望添加具有混和性之添加物, 例如可改良光阻膜之性能用之加成樹脂,可塑劑,黏接助 劑,穩定劑,著色劑,界面活性劑等之慣用之物。 進而,本發明之增強化學性型光阻組成物,爲了黏度 調整,可適宜配合有機溶劑。前述有機溶劑方面具體而言 ,可例舉丙酮,甲基乙基酮,環己酮,甲基異戊酮,2-庚酮等之酮類;乙二醇,乙二醇單乙酸酯,二乙二醇,二 乙二醇單乙酸酯,丙二醇,丙二醇單乙酸酯,二丙二醇或 二丙二醇單乙酸酯之單甲基醚,單乙基醚,單丙醚,單丁 醚或單苯基醚等之多價醇類及其衍生物;二噁烷般之環式 醚類;及乳酸甲酯,乳酸乙酯,乙酸甲酯,乙酸乙酯,乙 酸丁酯,丙酮酸乙酯,丙酮酸甲酯,甲氧基丙酸甲酯,乙 氧基丙酸乙酯等之酯類。該等可單獨使用,或混合2種以 上使用。 該等溶劑之使用量,例如使用旋轉塗佈法,爲了獲得 較佳爲20 // m以上之膜厚,則使增強化學性型光阻組成 物中固形成分濃度自30質量%成爲65質量%範圍爲佳。 固形成分濃度在不足3 0質量%之情形’在連接用端子之 製造上要獲得恰當的厚膜有困難’超過6 5質量%時組成 -24- 1266145 (21) 物之流動性會顯著惡化,在處理困難上,在旋轉塗佈法, 則無法獲得均勻的光阻薄膜。 接著’對正型增強化學性型光阻組成物之例加以說明 〇 增強化學性型光阻組成物爲正型之情形,交聯劑並不 需要。 又’ (Μ成分及(c )成分與負型之情形相同,(a )成分係’因酸可使鹼溶解性提高之樹脂。此(a )成分 方面’一般可作爲正型之增強化學性型光阻之基底樹脂使 用之樹脂的話’並無特別限定,可因應使用於曝光之光源 ,可自習知之物任意選擇使用。例如,以丙烯系樹脂爲主 成分,其羥基之至少一部份,可以因酸而解離之鹼溶解抑 制基取代之物或,以具有羥基苯乙烯構成單元之聚合物爲 主成分,其羥基之至少一部份,可以因酸所解離之鹼溶解 抑制基取代爲佳。 在特佳之(a)成分方面,可由具有與上述負型同樣 之(乙)羥基苯乙烯構成單元之聚合物,(丙)丙烯系樹 脂所選出之1種以上之樹脂所成,其羥基之至少一部份, 可例示以因酸而解離之鹼溶解抑制基所取代者。此係,因 爲要控制塗布性,顯影速度爲容易。 在因酸之作用而解離之鹼溶解抑制基方面,可例舉, 選自三級丁氧基,三級戊氧基等之第3級烷基氧基;四氫 吡喃氧基,四氫呋喃氧基等之環狀縮醛氧基;乙氧乙基氧 基,甲氧丙氧基等之鏈狀縮醛氧基;環己氧基,環戊基氧 -25- (22) 1266145 基等之環院基氧基;1-甲基環己氧基,1-乙基環院基氧 基等之1 一烷基一環烷基氧基;1-甲基金剛烷氧基,1 -乙基金剛烷氧基等之1 -烷基-聚環烷基氧基等之,至少 一種爲佳。 又,進而,在(a )成分,可以物理,化學特性予以 適度的控制之目的,.來含有其他之樹脂成分。例如可例舉 與上述負型相同之(甲)酚醛淸漆樹脂,(丁)乙烯樹脂 在上述負型之例中,除去交聯劑及(a )成分之,(b )成分及(c )成分,其他之成分可使用相同之物。 本發明之增強化學性型光阻組成物,在支持體上,並 ^ 無特別限定,但較佳爲20// m以上,更佳爲20〜150// m ,再佳爲30〜120//m,進而特佳爲55〜75//m膜厚之光 阻層之形成爲恰當。又,在光阻組成物中因含有防銹劑, 故,尤以在至少上面側之表面之一部份使用銅之支持體上 形成光阻層爲適合。 φ 接著,本發明之光阻層層合體係,在支持體上,塗布 前述增強化學性型光阻組成物,使光阻層層合者。 支持體方面,並無特別限定,可使用習知之物,可例 示例如,電子零件用之基板或,對此以所定之配線圖型所 形成者等。 該基板方面,可例舉例如,矽,氮化矽,鈦,鉬,鈀 ,鈦鎢,銅,鉻,鐵,鋁等之金屬製基板或玻璃基板等。 在配線圖型之材料方面,可使用例如銅,鍍錫,鉻,鋁, -26- 1266145 (23) 鎳,金等。 尤其是,在基板或配線圖型等,在支持體之至少上面 側之表面之一部份使用銅之情形,習知,與銅接觸部分之 增強化學性型光阻之作用會因銅被阻礙,在其一部分產生 顯影不良,而添加防銹劑,可獲得穩定的光阻層層合體, 可獲得良好的顯影輪廓。 本發明之增強化學性型光阻組成物之調製,例如,可 使上述成分不僅以通常方法混合,攪拌,亦可因應必要使 用溶解器,均化器,3輪軋製機(roll mill )等之分散機 予以分散,混合。又,在混合後,進而使用篩孔,膜過濾 器等予以過濾。 本發明之光阻層層合體,可由例如,以下之方式製造。 亦即,將如上述調製之增強化學性型光阻組成物之溶液塗 布於基板上,藉由加熱使溶劑除去,而可形成所望之塗膜 。在被處理基板上之塗布方法方面,可採用旋轉塗佈法, 輥塗布法,網孔印刷法,塗布機法(a p p 1 i c a t 〇 r )法等之 方法。本發明之組成物之塗膜之預烘烤條件,因組成物中 之各成分之種類,配合比率,塗布膜厚等而不同,但,通 常爲70〜130 °C,較佳爲80〜120 °C,2〜60分左右。 光阻層之膜厚,並無特別限定,但,較佳爲20 // m 以上,更佳爲20〜150//m,再佳爲30〜120#m,進而較 佳爲55〜75 // m之範圍爲所望。 在使用如此所得之光阻層層合體,形成光阻圖型時, 例如,在使用負型增強化學性型光阻之情形,在所得之光 -27- 1266145 (24) 阻層,透過所定圖型之光罩,將輻射線,例如波長3 Ο 0〜 5 0 0 nm之紫外線或可視光線予以選擇性照射(曝光)。 在該等輻射線之線源方面,可使用低壓水銀燈,高壓水銀 燈’超高壓水銀燈,金屬鹵化物燈,氣氣體雷射等。在此 所謂輻射線,係指紫外線,可視光線,遠紫外線,X線, 電子線等之意。輻射線照射量,可因組成物中之各成分之 種類’配合量,塗膜之膜厚等而異,例如在使用超高壓水 銀燈之情形,爲1 0 0〜2 0 0 0 m J / c m2。 接著,在曝光後,藉由使用公知方法予以加熱,可促 進酸之發生與擴散,可使此曝光部分之光阻層之鹼溶解性 變化。 接著,例如,使所定之鹼性水溶液作爲顯影液使用, 將不要之部分予以溶解,除去以獲得所定之光阻圖型。在 顯影液方面,可使用例如氫氧化鈉,氫氧化鉀等之鹼類之 水溶液。 又在前述鹼類之水溶液可將添加甲醇,乙醇等水溶性 有機溶劑或界面活性劑適當量之水溶液作爲顯影液使用。 顯影時間,會因組成物各成分之種類,配合比率,組 成物之乾燥膜厚而異,但通常爲1〜30分,又顯影之方法 可以旋轉法,浸漬法,浸置,噴灑顯影法等之任一種。在 顯影後,進行30〜90秒流水洗淨,可使用***或烤爐等 予以乾燥。 接著,在如此所得之光阻圖型之非光阻部(以鹼顯影 液除去之部分),例如可以電鍍等使金屬等之導體埋入, •28- (25) 1266145 而可形成金屬柱體或凸塊等之連接用端子。 使該等連接用端子形成於其中之非光阻部之尺寸,較 佳爲,寬5〜200//m,深10〜200//m。藉由本案組成物 可使尤其是長寬比2以上之光阻圖型良好的形成,藉此可 形成長寬比2以上之非光阻圖型。若使用本案組成物,則 長寬比1 〇之光阻圖型及根據此形成之非光阻圖型之形成 亦可行。習知之寬2 5 // m左右大小之非光阻部之形成, 係如本願般不加入防銹劑,亦可形成極耐實用之物,如上 述般之高精度的寬,高之尺寸之非光阻部,並無法在習知 方法形成可耐實用之物。但本案,可藉由防銹劑之使用, 來實現此高精度之非光阻部之形成。 另外,電鍍處理方法並無特別限制,可採用習知之各 種方法。在電鍍液方面,尤其是銲錫電鍍,銅電鍍液可恰 當使用。 所殘留之光阻圖型,最後,可依照一定方法,使用剝 離液等除去。 【實施方式】 以下,本發明係以實施例及比較例進而具體說明,但 本發明並非限定於該等之例。 依照下述之合成例,來合成樹脂成分。 [合成例1 ] 〈(A — 1 )酚醛淸漆樹脂之合成〉 -29- (26) 1266145 將間甲酚與對甲酚以質量比60 : 40之比率混合,對 此添加甲醛水,使用草酸觸媒依照常法予以縮合以獲得甲 酚酚醛淸漆樹脂。相對於此樹脂實施分餾處理,將低分子 領域予以切割,以獲得質量平均分子量8,000之酚醛淸漆 樹脂。使此樹脂作爲(A - 1 )。 [合成例2] 〈具有(A — 2)羥基苯乙烯構成單元之聚合物之合成〉 將附有攪拌裝置,還流器,溫度計,滴下槽之燒瓶予 以氮取代後’裝入作爲溶劑之丙二醇甲基醚乙酸酯,開始 進行攪拌。 其後<,使溶劑之溫度上升至80 °C。在滴下槽聚合觸 媒係裝入2 ’ 2 > -偶氮異丁腈,構成單元係裝入,羥基 苯乙烯單元75質量%與苯乙烯單元25質量%,使聚合觸 媒攪拌至溶解爲止後,將此溶液在燒瓶內均勻滴下3小時 ’接著在8 0 °C,進行5小時聚合。其後,冷卻至室溫爲 止,獲得成爲(A )成分之樹脂。 相對於此樹脂實施分餾處理,獲得質量平均分子量 3,〇〇〇 之樹脂(A— 2)。 [合成例3 ] 〈(A - 3 )丙烯系樹脂之合成〉 除了構成單元係使用,2—甲氧乙基丙烯酸酯130質 量份’苄基甲基丙烯酸酯5〇質量份,及丙烯酸20質量份 -30- 1266145 (27) 以外’其他與合成例2相同,獲得質量平均分子量20,000 之樹脂(A — 3 )。 [合成例4] 〈(A — 4)乙烯樹脂之合成〉 使用旋轉汽化器(rotary evaporator),將聚(乙嫌 甲基醚)(質量平均分子量50,000)之甲醇溶液(東京化 成工業公司製,濃度50質量%)在丙二醇單甲基醚乙酸 酯進行溶劑取代,獲得濃度5 0質量%之溶液(A - 4 )。 [合成例5] 〈(A — 5 )因酸之作用使得對鹼之溶解性增大之樹脂之 合成〉 除了構成單元係使用金剛烷丙烯酸酯構成單元5 0質 量%,及2—乙氧乙基丙烯酸酯構成單元50質量%以外 ,其他則與合成例2同樣,獲得質量平均分子量25 0,000 之樹脂(A — 5 )。 [實施例1〜9][比較例1] 〈厚膜用增強化學性型光阻組成物之調整〉 將表1所示各成分混合於丙二醇單甲基醚乙酸酯,成 爲均勻溶液後,通過孔徑1 // m之膜過濾器予以過濾,獲 得厚膜用增強化學性型正型光阻組成物。另外,表1所示 各成分之記號之內容係如下述。 -31 - 1266145 (28) (B — 1 ):下述化學式所示化合物 〔化8〕 C4H9 -S-〇-N = = N -〇-^- G4H9 °2 CN\^ CN °2 (C — 1 ) 1,3,5 —三畊一 2,4,6 —三硫醇 (C 一 2)1 —硫甘油 (C 一 3 )三戊基胺 (D — 1 )交聯劑:六甲氧甲基化三聚氫胺(三和化 學公司製,商品名:NikaluckMw-100) 關於所得之厚膜用增強化學性型正型光阻組成物,則 進行下述評價。 •感光性 在5英吋之矽晶圓上,形成各種膜厚之塗膜,藉由解 像度測定用之圖型透過光罩,使用步進器(Nikon公司製 ,NSR-2005ilOD)在 100 〜1 0,000 mJ/cm2 之範圍分割, 曝光。使其以顯影液(商品名PMER系列,P - 7G,東京 應化工業公司製)顯影。此後,以流水洗淨,進行氮吹氣 ,獲得圖型狀硬化物。對此以顯微鏡觀察,形成長寬比2 以上之圖型,來測定無法認定殘渣之曝光量,亦即對形成 圖型爲必要之最低限之曝光量。 顯影性 -32- 1266145 (29) 在5英吋之銅濺鍍晶圓上使用旋轉器,使各組成物, 成爲膜厚約20//m之方式,在1800 rpm塗布25秒後,在 1 1 〇 °C,於熱板上預烘烤6分,來形成厚膜光阻層合體。 使具有膜厚約65 // m之塗膜之光阻層合體以下述方 式形成。在800 rpm進行25秒塗布,在110t於熱板上 進行預烘烤1分,進而在800 rpm進行25秒塗布後,在 1 1 〇°C進行預烘烤1 2分,來形成厚膜光阻層合體。 又,具有膜厚約120// m之塗膜之光阻層合體係以下 述之方式形成。在800 rpm塗布25秒後,於1 10°C在熱 板上預烘烤1分,進而在5 00 rpm塗布25秒後,在110 °C 於熱板上預烘烤1分,進而在5 00 rpm進行25秒塗布後 ’於110 °C進行20分預烘烤以形成厚膜光阻層合體。 將上述所得之厚膜光阻層合體,使用步進器(Nikon 公司製,NSR-2005ilOD ),使解像度測定用之圖型透過 光罩,各自以100〜1 0,000 mJ/cm2之範圍進行階段性之 紫外線曝光。在曝光後,於70 °C加熱5分,使其以顯影 液(商品名PMER系列,P— 7G,東京應化工業公司製) 顯影。 此後,以流水洗淨,進行氮吹氣來獲得圖型狀硬化物 。對此以顯微鏡觀察,將顯影•解像性以下述之評價基準 來判定。 A :長寬比2以上之圖型則以前述任一種之曝光量形 成’在無法認定殘渣之情形。 C:長寬比不足2之圖型並不形成’或殘渣被認定之 -33- 1266145 (30) 情形。 另外,長寬比係顯示,(圖型上之光阻高度+圖型上 之光阻寬度)。 •光阻形狀 將具有以「顯影•解像性評價」所得之圖型狀硬化物 之基板作爲試驗體,來觀察試驗體上所形成之圖型狀硬化 物之狀態,將圖型狀硬化物之形狀以下述之評價基準判定 〇 A :矩形之光阻圖型可獲得。 B :僅有逆錐形形狀之矩形光阻圖型可獲得。 C :矩形之光阻圖型無法獲得。 •遮蔽能 以與「顯影•解像性評價」同樣之方法,在銅濺鍍晶 圓上來形成圖型狀硬化物,將光阻圖型之形狀以目視觀察 ’以下述之評價基準判定。 A :可形成光阻圖型。 C :產生殘膜。 關於實施例1〜9,及比較例丨所調製之光阻組成物 ’進行上述之各試驗來評價。結果如袠2所示。另外關於 實施例3係使膜厚變化進行評價。 -34- (31) 1266145 〔表1〕 (單位:質量份) 實施例 比較 例 1 2 3 4 5 6 7 8 9 1 A- 1 90 70 70 70 70 70 60 70 A-2 20 20 20 20 20 90 10 20 A-3 10 A-4 10 A-5 100 B-1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 C- 1 0.3 0.1 0.3 1 0.3 0.3 0.3 C-2 0.3 C-3 0.3 D- 1 10 10 10 10 10 10 10 10 10 -35- (32)1266145 比較例 'Ο 1 1 1 υ 實施例 ON ιη 3000 < < < 00 ν〇 1000 <d < < 卜 Ό 1000 < < < Ό 1000 < < < νο 1000 < < < 寸 ν〇 1000 < < < m r-H 1500 < m < (T) Ό 1000 < < < cn 500 < < < (N ν〇 1000 < < < τ-Η ν〇 1000 < < < 膜厚 感光性 (mJ/cm2) 顯影性 光阻形 狀 HD <ΠΕIn the case of a benzotriazole-based compound, specifically, for example, benzotriazole, 5,6-dimethylbenzotriazole, fluorene monohydroxybenzotriazole, fluorene monomethylbenzopyrene, 1 Monoaminobenzotriazine, 1 phenylbenzotriazine, 1 monomethyl benzodiazole, 1 benzotriazole carboxylic acid methyl, 5-benzotriazole carboxylic acid, 1 A Oxygen-benzotriazole, 1-(2,2-dihydroxyethyl)-benzobisazole, 1-(2,3-dihydroxypropyl)benzotriazole, or "Ilkamate" series in Chiba Specially used by specialty chemical companies, for example 2'2~{[(4-methyl-1H-benzotriazole-!-yl)methyl]imino}diethanol, 2, wide -U(5-methyl-1H-benzodioxin-l-yl)methyl]imino}diethanol, 2, — {[(4-a-21 - 1266145 (18) yl- 1H- Benzotriazole-1-yl)methyl]imidopyridinium di-ethane, or 2,2 {[(4 monomethyl-1H-benzotriazol-1-yl)methyl]imido] Dipropane and the like. Among these, 1-(2,3-dihydroxypropyl)-benzotriazole, 2,2,-{[(4-methyl-1H-benzotriazol-1-yl)methyl] Imino]diethanol, 2,2-{{(5-methyl-1H-benzotriazol-1 mono)methyl]imino}diethanol can be suitably used. One type or two or more types of benzotriazole-based compounds can be used. In the above sulfur-containing compound, dithiodiglycerol [S (CH2CH(OH)CH2(OH)) 2], bis(2,3-dihydroxypropylthio)ethene [CH2CH2 (SCH2CH (OH) CH2) can be exemplified. ( OH ) ) 2],3 -(2,3 -dihydroxypropylthio)-sodium 2-methylpropanesulfonate [CH2 ( OH ) CH ( OH) CH2SCH2CH ( CH3 ) CH2S03Na], 1 -thioglycerol [HSCH2CH(OH) CH2 ( OH ) ], 3 - thiol-sodium 1-propane sulfonate [HSCH2CH2CH2S03Na], 2-thiol-ethanol [HSCH2CH2 (OH)], thioacetic acid [HSCH2C02H], and 3 —Hexylthio-1-propanol [HSCH2CH2CH20H], 1,3,5-three tillage-2,4,6-trithiol. Among these, 1-monothioglycerol, 1,3,5-three tillage-2,4,6-trithiol, thioacetic acid, and the like can be suitably used. One or two or more kinds of the components (c) can be used. The component (c) is preferably in the range of 0.01 to 5 parts by mass, more preferably in the range of 0.1 to 1 part by mass, per 100 parts by mass of the component (a). When the content of the component (c) is less than 〇. 质量1 parts by mass, there is a case where a high-precision photoresist pattern cannot be obtained, and when it exceeds 5 parts by mass, the adhesion between the photoresist pattern and the substrate is lowered. Hey. -22- 1266145 (19) In the case where the chemical-resistant resist composition is a negative type, in addition to the above components, a crosslinking agent is further contained. The crosslinking agent used in the present invention is not particularly limited, and a crosslinking agent for any of the well-known chemically-reactive negative-type photoresist compositions can be suitably used. For example, a melamine resin, a urea resin, a guanamine resin, a glycoluril-a waking resin, an amber amide-formaldehyde resin, an ethylene urea-formaldehyde resin, etc., but particularly an alkoxymethylation can be used. An alkoxymethylated amino resin such as a trihydroamine resin or an alkoxymethylated urea resin can be suitably used. The alkoxymethylated amino resin is, for example, a condensate obtained by reacting a polyamine or urea with a formalin in a boiling aqueous solution, such as methyl alcohol, ethyl alcohol, propanol, butanol or isopropanol. The lower alcohol is etherified, and then the reaction liquid is cooled and precipitated to be produced. In the above alkoxymethylated amino resin, specifically, a methoxymethylated melamine resin, an ethoxymethylated melamine resin, a propoxymethylated melamine resin, a butoxymethylated melamine resin, and the like may be mentioned. Oxymethylated® resin, ethoxymethylated urea resin, propoxymethylated urea resin, butoxymethylated urea resin. The alkoxymethylated amino resins may be used singly or in combination of two or more. In particular, the alkoxymethylated melamine lipoester has a small dimensional change with respect to the change in the amount of irradiation of the radiation, and is preferable because a stable photoresist pattern can be formed. Among them, methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethyl t hydrazine polyamine resin and butoxymethylated melamine resin are preferred. The crosslinking agent is preferably contained in an amount of from 1 to 30 parts by mass based on 1 part by mass of the total of the components (a), (b) and (c). Crosslinking agent-23- 1266145 (20) When the amount is less than 1 part by mass, the plating resistance, chemical resistance, and adhesion of the obtained film may be lowered or the shape of the formed bump may be poor. When the amount exceeds 30 parts by mass, development failure occurs during development, which is not preferable. In the reinforced chemical-type resist composition of the present invention, an additive having a blending property, such as an additive resin for improving the performance of the photoresist film, a plasticizer, can be added in a range that does not impair the essential characteristics. , adhesive additives, stabilizers, colorants, surfactants and the like. Further, in the reinforced chemical resist composition of the present invention, an organic solvent can be suitably blended for viscosity adjustment. Specific examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, and the like; ethylene glycol, ethylene glycol monoacetate, Diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol or dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or Polyvalent alcohols such as monophenyl ether and derivatives thereof; dioxane-like cyclic ethers; and methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, ethyl pyruvate An ester of methyl pyruvate, methyl methoxypropionate, ethyl ethoxy propionate or the like. These may be used singly or in combination of two or more. The amount of the solvent used is, for example, a spin coating method, and in order to obtain a film thickness of preferably 20 // m or more, the solid content concentration in the reinforced chemical resist composition is from 30% by mass to 65% by mass. The range is good. In the case where the solid content concentration is less than 30% by mass, it is difficult to obtain an appropriate thick film in the production of the terminal for connection. When the content exceeds 65 mass%, the composition of the composition -24-1266145 (21) is significantly deteriorated. In the processing difficulty, a uniform photoresist film cannot be obtained by the spin coating method. Next, an example of a positive-type enhanced chemical resist composition will be described. 增强 A chemical-type resist composition is a positive type, and a crosslinking agent is not required. Further, (the bismuth component and the (c) component are the same as the negative one, and the component (a) is a resin which can improve the alkali solubility due to the acid. The component (a) can generally be used as a positive type to enhance chemical chemistry. The resin used for the base resin of the type of photoresist is not particularly limited, and can be used arbitrarily according to the light source for exposure, for example, a propylene resin as a main component and at least a part of a hydroxyl group thereof. An alkali-dissolving inhibitor-substituted material which may be dissociated by an acid or a polymer having a hydroxystyrene structural unit as a main component, and at least a part of a hydroxyl group thereof may be substituted by an alkali-dissolving inhibiting group which is dissociated by an acid. In terms of the component (a), it may be composed of a polymer having a (i) hydroxystyrene constituent unit similar to the above negative type, and a resin selected from the group consisting of a (propylene) propylene resin, and a hydroxyl group thereof. At least one part can be exemplified by a base dissolution inhibiting group which is dissociated by an acid. This is because the coating speed is controlled, and the development speed is easy. In the dissolution of the alkali due to the action of acid The base group may, for example, be a tertiary alkyloxy group selected from a tertiary butoxy group, a tertiary pentyloxy group or the like; a cyclic acetaloxy group such as a tetrahydropyranyloxy group or a tetrahydrofuranyloxy group; a chain acetaloxy group such as ethoxyethyloxy or methoxypropoxy; a cyclohexyloxy group of cyclohexyloxy, cyclopentyloxy-25-(22) 1266145; 1-methyl a mono-alkyl-cycloalkyloxy group such as a cyclohexyloxy group, a 1-ethylcyclohexyloxy group, a 1-methyladamantyloxy group, a 1-ethyladamantyloxy group or the like, and an alkyl group. Further, at least one of a polycycloalkyloxy group and the like is preferable. Further, the component (a) may be appropriately controlled by physical and chemical properties, and may contain other resin components. For example, the above-mentioned components may be mentioned. (A) phenolic enamel resin, (butyl) vinyl resin in the above negative examples, the cross-linking agent and (a) component, (b) component and (c) component, other components may be The reinforced chemical resist composition of the present invention is not particularly limited as long as it is on the support, but is preferably 20//m or more, more preferably 20 to 150//m. It is suitable for the formation of a photoresist layer of 30 to 120 / / m, and particularly preferably a film thickness of 55 to 75 / / m. Further, since the photoresist composition contains a rust inhibitor, it is particularly at least It is suitable to form a photoresist layer on one of the surface of the side using a copper support. φ Next, the photoresist layer lamination system of the present invention is coated on the support with the above-mentioned enhanced chemical type photoresist composition. The support layer is not particularly limited, and a conventional one can be used, and examples thereof include a substrate for an electronic component or a shape formed by a predetermined wiring pattern. For example, a metal substrate such as ruthenium, tantalum nitride, titanium, molybdenum, palladium, titanium tungsten, copper, chromium, iron, or aluminum, or a glass substrate can be used. For the material of the wiring pattern, for example, copper can be used. Tin, chrome, aluminum, -26- 1266145 (23) Nickel, gold, etc. In particular, in the case of a substrate or a wiring pattern or the like, copper is used in a part of the surface of at least the upper side of the support, and it is known that the effect of the enhanced chemical resistance of the contact portion with the copper is hindered by copper. A development defect is generated in a part of the film, and a rust inhibitor is added to obtain a stable photoresist layer laminate, and a good development profile can be obtained. In the preparation of the chemistive resistive composition of the present invention, for example, the above components may be mixed not only by a usual method, but also by a dissolver, a homogenizer, a roll mill, or the like. The disperser is dispersed and mixed. Further, after mixing, a sieve, a membrane filter or the like is further used for filtration. The photoresist layer laminate of the present invention can be produced, for example, in the following manner. Namely, a solution of the enhanced chemical resist composition prepared as described above is applied onto a substrate, and the solvent is removed by heating to form a desired coating film. As the coating method on the substrate to be processed, a method such as a spin coating method, a roll coating method, a mesh printing method, or a coater method (a p p i i c a t 〇 r) method can be employed. The prebaking conditions of the coating film of the composition of the present invention differ depending on the type of each component in the composition, the blending ratio, the coating film thickness, etc., but are usually 70 to 130 ° C, preferably 80 to 120. °C, about 2~60 minutes. The film thickness of the photoresist layer is not particularly limited, but is preferably 20 // m or more, more preferably 20 to 150/m, still more preferably 30 to 120 #m, and still more preferably 55 to 75 / The range of /m is expected. When the photoresist layer laminate thus obtained is used to form a photoresist pattern, for example, in the case of using a negative-type enhanced chemical type photoresist, the obtained light -27-1266145 (24) resist layer is transmitted through the predetermined pattern. A type of reticle that selectively illuminates (exposed) radiation, such as ultraviolet light or visible light having a wavelength of 3 5 0 to 500 nm. In terms of the source of such radiation, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, gas-gas lasers, and the like can be used. Here, the term "radiation line" means ultraviolet light, visible light, far ultraviolet light, X-ray, electronic wire, etc. The amount of radiation exposure may vary depending on the type of each component in the composition, the film thickness of the coating film, and the like, for example, in the case of using an ultrahigh pressure mercury lamp, it is 1 0 0 to 2 0 0 m J / c. M2. Then, after the exposure, heating by a known method promotes the generation and diffusion of the acid, and the alkali solubility of the exposed photoresist layer can be changed. Next, for example, a predetermined alkaline aqueous solution is used as a developing solution, and an unnecessary portion is dissolved and removed to obtain a predetermined photoresist pattern. As the developer, an aqueous solution of a base such as sodium hydroxide or potassium hydroxide can be used. Further, an aqueous solution containing a water-soluble organic solvent such as methanol or ethanol or an appropriate amount of a surfactant may be used as a developing solution in the aqueous solution of the above-mentioned base. The development time varies depending on the type and composition ratio of each component of the composition, and the dry film thickness of the composition varies, but it is usually 1 to 30 minutes, and the development method can be a spin method, a dipping method, a dipping method, a spray developing method, or the like. Any of them. After development, it is washed with running water for 30 to 90 seconds, and it can be dried using an air gun or an oven. Then, in the non-resistance portion (the portion removed by the alkali developing solution) of the photoresist pattern thus obtained, for example, a conductor such as a metal can be buried by electroplating or the like, and 28-(25) 1266145 can be formed to form a metal cylinder. Or a terminal for connection such as a bump. The size of the non-photosensitive portion in which the terminals for connection are formed is preferably 5 to 200 / / m in width and 10 to 200 / / m in depth. According to the composition of the present invention, a photoresist pattern having an aspect ratio of 2 or more can be formed favorably, whereby a non-resistive pattern having an aspect ratio of 2 or more can be formed. If the composition of the present invention is used, it is also possible to form a photoresist pattern having an aspect ratio of 1 及 and a non-resistive pattern formed therefrom. The formation of the non-resistive part of the size of 2 5 // m or so is not to add a rust preventive agent as it is intended, and it can also form a highly practical thing, such as the above-mentioned high-precision width and height. The non-resistive part cannot form a practical thing in a conventional method. However, in this case, the formation of the high-precision non-resistive portion can be achieved by the use of a rust preventive. Further, the plating treatment method is not particularly limited, and various conventional methods can be employed. In the case of electroplating solutions, especially solder plating, copper plating solutions can be used just right. The residual photoresist pattern is finally removed by using a stripping solution or the like according to a certain method. [Embodiment] Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the examples. The resin component was synthesized in accordance with the following synthesis examples. [Synthesis Example 1] Synthesis of <(A-1) phenolic enamel resin> -29- (26) 1266145 Mix m-cresol with p-cresol at a mass ratio of 60:40, add formaldehyde water, use The oxalic acid catalyst is condensed according to a conventional method to obtain a cresol novolac lacquer resin. The fractionation treatment was carried out with respect to this resin, and the low molecular field was cut to obtain a phenolic enamel resin having a mass average molecular weight of 8,000. This resin was made into (A - 1 ). [Synthesis Example 2] <Synthesis of a polymer having (A-2) hydroxystyrene constituent unit> A flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank was replaced with nitrogen, and then charged as a solvent of propylene glycol A. The base ether acetate was stirred. Thereafter, <, the temperature of the solvent was raised to 80 °C. 2' 2 > - azoisobutyronitrile was placed in the dropping polymerization catalyst, and the constituent unit was charged. The hydroxystyrene unit was 75 mass% and the styrene unit was 25 mass%, and the polymerization catalyst was stirred until dissolved. Thereafter, the solution was uniformly dropped in the flask for 3 hours', followed by polymerization at 80 ° C for 5 hours. Thereafter, the mixture was cooled to room temperature to obtain a resin which was a component (A). The resin was subjected to a fractionation treatment to obtain a resin having a mass average molecular weight of 3, yttrium (A-2). [Synthesis Example 3] Synthesis of <(A - 3 ) propylene-based resin> In addition to the constituent unit system, 2-methoxyethyl acrylate 130 parts by mass of 'benzyl methacrylate 5 parts by mass, and acrylic acid 20 mass Parts -30- 1266145 (27) Other than the same as in Synthesis Example 2, a resin (A-3) having a mass average molecular weight of 20,000 was obtained. [Synthesis Example 4] <Synthesis of (A-4) Vinyl Resin> A methanol solution of poly(ethyl methacrylate) (mass average molecular weight: 50,000) (manufactured by Tokyo Chemical Industry Co., Ltd., concentration) using a rotary evaporator 50% by mass) was subjected to solvent substitution in propylene glycol monomethyl ether acetate to obtain a solution (A - 4 ) having a concentration of 50% by mass. [Synthesis Example 5] <(A-5) Synthesis of Resin which Increases Solubility to Alkali by Effect of Acid> In addition to the constituent unit, adamantane acrylate constituent unit 50% by mass, and 2-ethoxyB A resin (A-5) having a mass average molecular weight of 25,000 was obtained in the same manner as in Synthesis Example 2 except that the acrylate structural unit was 50% by mass. [Examples 1 to 9] [Comparative Example 1] <Adjustment of Reinforcing Chemical Type Photoresist Composition for Thick Film> After each component shown in Table 1 was mixed with propylene glycol monomethyl ether acetate to form a homogeneous solution, Filtration was carried out through a membrane filter having a pore size of 1 // m to obtain a chemically-enhanced positive photoresist composition for a thick film. Further, the contents of the symbols of the respective components shown in Table 1 are as follows. -31 - 1266145 (28) (B - 1 ): Compound represented by the following chemical formula [Chemical 8] C4H9 -S-〇-N = = N -〇-^- G4H9 °2 CN\^ CN °2 (C — 1) 1,3,5 - three tillage 2,4,6-trithiol (C-2) 1 -thioglycerol (C-3) tripentylamine (D-1) crosslinker: hexamethoxy The hydrazine triamine (trade name: Nikaluck Mw-100, manufactured by Sanwa Chemical Co., Ltd.) The following evaluation was carried out on the obtained chemically-resistant positive-type photoresist composition for thick film. • The photosensitive film is formed on a wafer of 5 inches in thickness, and a film having various film thicknesses is formed. The pattern for resolution measurement is transmitted through the mask, and a stepper (NSR-2005ilOD, manufactured by Nikon Co., Ltd.) is used at 100 to 1 The range of 0,000 mJ/cm2 is divided and exposed. This was developed with a developing solution (trade name: PMER series, P-7G, manufactured by Tokyo Ohka Kogyo Co., Ltd.). Thereafter, it was washed with running water, and nitrogen gas was blown to obtain a pattern-like cured product. This was observed by a microscope to form a pattern having an aspect ratio of 2 or more, and the exposure amount of the residue could not be determined, that is, the exposure amount necessary for the formation of the pattern. Developability - 32 - 1266145 (29) Using a rotator on a 5 inch copper sputter wafer, the composition was applied to a film thickness of about 20/m, and applied at 1800 rpm for 25 seconds, at 1 1 〇 ° C, pre-baked on the hot plate for 6 minutes to form a thick film photoresist laminate. A photoresist laminate having a coating film having a film thickness of about 65 // m was formed in the following manner. The film was applied at 800 rpm for 25 seconds, pre-baked on a hot plate at 110 Torr for 1 minute, and further coated at 800 rpm for 25 seconds, and then pre-baked at 12 ° C for 12 minutes to form thick film light. The barrier layer is combined. Further, a photoresist laminated system having a coating film having a film thickness of about 120 / / m was formed as follows. After coating at 800 rpm for 25 seconds, pre-bake 1 minute on a hot plate at 10 ° C, and then 25 seconds at 500 rpm, pre-bake 1 minute on a hot plate at 110 ° C, and then at 5 After 20 seconds of coating at 00 rpm, 20 minutes pre-baking was performed at 110 ° C to form a thick film photoresist laminate. The thick film resist laminate obtained above was passed through a mask using a stepper (NSR-2005ilOD, manufactured by Nikon Co., Ltd.), and each of the layers was passed through a mask at a range of 100 to 10,000 mJ/cm 2 . UV exposure. After the exposure, the mixture was heated at 70 ° C for 5 minutes, and developed with a developing solution (trade name: PMER series, P-7G, manufactured by Tokyo Ohka Kogyo Co., Ltd.). Thereafter, it was washed with running water and subjected to nitrogen blowing to obtain a patterned cured product. This was examined by a microscope, and the development and resolution were determined by the following evaluation criteria. A: A pattern having an aspect ratio of 2 or more is formed by the exposure amount of any of the above-mentioned cases where the residue cannot be determined. C: The pattern with an aspect ratio of less than 2 does not form 'or the residue is identified as -33-1266145 (30). In addition, the aspect ratio is displayed (the height of the photoresist on the pattern + the width of the photoresist on the pattern). • The resist shape has a substrate having a patterned cured product obtained by "developing and resolution evaluation" as a test piece, and the state of the patterned cured product formed on the test piece is observed, and the pattern-shaped cured product is observed. The shape was judged by the following evaluation criteria: 矩形A: Rectangular photoresist pattern is available. B: A rectangular photoresist pattern having only an inverse tapered shape is available. C: Rectangular photoresist pattern is not available. • Shading The pattern-shaped cured product was formed on the copper sputtering crystal circle in the same manner as in the "development and resolution evaluation", and the shape of the photoresist pattern was visually observed. A: A photoresist pattern can be formed. C: Residual film is produced. The examples of the examples 1 to 9 and the photoresist composition prepared in the comparative example were evaluated by the respective tests described above. The result is shown in 袠2. Further, in Example 3, the film thickness change was evaluated. -34- (31) 1266145 [Table 1] (Unit: parts by mass) Example Comparative Example 1 2 3 4 5 6 7 8 9 1 A- 1 90 70 70 70 70 70 60 70 A-2 20 20 20 20 20 90 10 20 A-3 10 A-4 10 A-5 100 B-1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 C- 1 0.3 0.1 0.3 1 0.3 0.3 0.3 C-2 0.3 C-3 0.3 D- 1 10 10 10 10 10 10 10 10 10 -35- (32) 1266145 Comparative Example 'Ο 1 1 1 实施 Example ON ιη 3000 <<< 00 ν〇1000 <d << Ό 1000 <<< Ό 1000 <<< νο 1000 <<< 寸 ν〇1000 <<< m rH 1500 < m < (T) Ό 1000 <<< cn <<<< τ-Η ν〇1000 <<< Film thickness sensitivity (mJ/cm2) developable resist shape HD <
-36- (33) 1266145 由表2之結果可知’與本發明有關之實施例中,任一 之評價均爲良好。 〔產業上之利用可能性〕 如以上之詳細說明,根據本發明係提供,在輻射線照 射前鹼溶解性不致變化之穩定的增強化學性型光阻組成物 ,及使該光阻組成物層合於支持體之光阻層層合體,使用 此之光阻圖型製造方法及連接用端子製造方法。因此,本 發明在工業上極爲有用。-36- (33) 1266145 It is understood from the results of Table 2 that in the examples relating to the present invention, any of the evaluations was good. [Industrial Applicability] As described in detail above, according to the present invention, there is provided a stable chemical-resistant resist composition which does not change in alkali solubility before irradiation of radiation, and a photoresist composition layer The photoresist layer laminate to be used in the support, the photoresist pattern manufacturing method and the terminal manufacturing method for the connection are used. Therefore, the present invention is extremely useful industrially.
-37--37-
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